Anthraquinone derivatives



Patented Sept. 25, 1934 PATENT OFFICE ANTHRAQUINONE j DERIVATIVESHermann Hauser, Basel, and Max Bummer, Riehen, near Basel, Switzerland,assignors to firm Society of Chemical Industry in Basle,

Basel, Switzerland No Drawing. Application June 21, 1932, Serial No.618,582. In Switzerland July 2, 1931 a 3 Claims.

It has been found that compounds of the probable general formula inwhich R1 and R2 represent radicles capable of being vatted, at least oneof which is difierent from 1-anthraquinonyl, are valuable" anthraquinone derivatives. 7

These compounds may be made according to various processes. Thusforexample, 2 molecular proportions of similar or difierent' compoundseach containing one amino-group and capable of being vatted, .atleastone of which is different from l-amino-anthraquinone, may be caused toreact with 1 molecular proportion of 1:3- dihalogen-anthraquinone. Or 2molecular proportions of a 1:3-dihalogen-anthraquinone may be condensedwith 1 molecular proportion of a compound capable of being .vatted andcontaining at least 2 amino-groups, and the product thus obtainedtransformed with 2 molecular proportions of any compound capable ofbeing vatted, but containing at least one amino-group. Instead of the1:3-dihalogen-anthraquinones there may be used as initial products thecorresponding 1:3- diamino-anthraquinones,and on 1 molecular proportionof such a compound there may be caused to react 2 molecular proportionsof similar or different compounds, each containing one reactive halogenatom and capable of being vatted, at least one of which is differentfrom l-halogenanthraquinone. a 1:3-diamino-anthraquinone may becondensed Withl molecular proportion of a compound containing at least 2reactive halogen atoms and.-

atom.

The processes described above are preferably conducted in the presenceof a solvent of high Or 2 molecular proportions of.

boiling point, such as, for example, naphthalene,

nitrobenzene, trichloro'benzen'e in the presence of acid binding agents,such as, for instance, anhydrous sodium acetate, potassium acetate,calcined alkali-carbonates, copper oxide, mag-- nesium oxide, and in thepresence of catalysts, 'such as, for example, metallic copper and itscompounds.

The compounds obtained in the above described manner are, alreadydyestuffs themselves, but

they may also, serveas intermediate products for the manufacture offurther dyestufis. Especially -valuable dyestufis are obtained if theproducts obtained according to the described processes withanthraquinone derivatives are treated with condensing agents. There arethus formed compounds of the above probable formula in which probablythe carbon atom of the anthraquinone radicle R1 standing in 0-positionto the imino-group is bridge-like linked with the carbon atom of theanthraquinone radiclestandi-ng in 2-position to the same imino-group.

As condensing agents there come into consideration for exampleconcentrated sulfuric acid, chlorosulfonic acid and fluorsulfonic acid,aluminium chloride alone or mixed with alkali halides, or in thepresence of organic bases, or as ammonia double compound. In many casesit is advantageous to apply an after-treatment of the dyestuffsobtainedwith oxidizing agents, for example hypochlorite.

4 As 1:3-dihalogen anthraquinones which may be used in the'presentprocess, there come into consideration for example the1:3-dichloro-anthra-- quinone, the 1:3-dibromo-anthraquinone, the 1-chloro-3-bromo-anthraquinone, the 1-bromo-3- chloro-anthraquinone,Further also the 1:3- diamino-anthraquinone may be used in the presentprocess.

Compounds capable of being vatted containing benzanthrones, amino-pyranthrones; amino-' one each or at least two amino-group's and whichhalogen-dibenzpyrene-quinones, halogen-anthri mide-carbazoles, and thenitro derivatives of these compounds. I

In dyeing, the new anthraquinone derivatives which may be producedaccording to the present process yield valuable shades of very goodfastness properties. They may also be l edin dyeing in the form of theirleuco compounds, such as for instance in the form of their leuco esters.

The following examples illustrate the invention:

Example 1 V 7.2 parts by weight of 1:3dibromo-anthraquinone, 14 parts of1:5-monobenzoyldiamino-' anthraquinone, 8 parts of anhydrous sodium ace-I tate and 150 parts of nitrobenzene are heated to boiling for 6 hours,during which the acetic acid which is formed distils. The wholeis-filtered whilst still hot, the solid matter is washed withnitrobenzene and alcohol, and then extracted with boiling water,filtered and dried. There'are obtained 17.7 parts of a red-browncrystalline powder of the probable formula which, after precipitationfrom sulfuric acid of 96 per cent strength; at 0 C., yields oncotton'powerful red-brown dyeings of very good fastness properties. r

If in this example there is used instead of 1:5=monobenzoyl-diamino-anthraquinone the isomeric 14-monobenzoyl-diamino-anthraquinone there is obtained a product whichdyes cotton powerful currant shades.

' Example 2 ,18.3 parts of 1:3-dibromanthraquinone, 17.1 parts of -1 :5monobenzoyl diaminoanthraquinone, 10 parts f-anhydrous sodium acetate, 1part of copper acetate and 180 parts of nitrobenzene are heated toboiling for 3 hours in a refluxapparatus. The new compound which hasprobable formula separated is isolated by filtering the mixture whilststill hot, washed with nitrobenzene and alcohol, then boiled with water,filtered and dried. It is thus obtained in the form of small fine redneedles which dissolve in sulfuric acid of 97 per cent strength to anolive brown solution. The new compound still contains a reactive halogenatom which can be replaced by another residue in the following manner:

Parts The compound 8 waminoanthraquinone 3 Anhydrous sodium acetate 3Copper acetate 1 Nitrobenzene 100 'are heated to boiling for 18 hours ina reflux apparatus and the reaction product of the is isolated byfiltering whilst still hot. It is a red crystalline powder whichdissolves in sulfuric acid of 97 per cent strength to a green toolive-green solution. After the new dyestuif has been reprecipitatedfromits solution in concentrated sulfuric acid, it dyes cotton powerfulreddishbrown shades of very good fastness to washing and to chlorine. Bystirring this compound for a short while with chlorosulfonic acid at -55C., diluting the chlorosulfonic acid with sulfuric acid of per centstrength and pouring the whole onto ice there is obtained a new dyestuifof the probable formula which after treatment in known manner with a 7solution of sodium hypochlorite dyes cotton in a 3.6 parts of 1:3-dibromanthraquinone, 9.4 parts of amino-dibenzanthrone (obtainable bynitrating dibe'nzanthronexin nitrobenzene, recrystallizing the productfrom concentrated sulfuric acid, vatting it with simultaneous reductionand re-' covering the product fromthe vat), 5 parts of anhydrous sodiumacetate, 1 part of copper ace tate and 170 parts of nitrobenzeneare-heated to boiling for 22 hours in a reflux apparatus. The sparinglysoluble reaction product of the probable formula is isolated byfiltering the reaction mixture at 70 C. and is washed with nitrobenzene,then with alcohol and finally with boiling water. The new dyestufidissolves in sulfuric acid of 97 per cent strength to a red-violetsolution, from which bluegreen flakes are precipitated by pouring intowater. It dyes cotton dark green shades which are distinguished aboveall by their good fastness to chlorine.

Example 4 18.3 parts of 1:3-dibromanthraquinone, 17.1 parts of 1:4-monobenzoyl-diaminoanthraquinone, 10 parts of anhydrous sodiumacetate, 1 part of copper acetateand 180 parts of nitrobenzene areheated to boiling for 3 hours in a reflux apparatus; the nitrobenzene isthen expelled by distillation with steam and the'product is isolated byfiltering the residue of :the distillation. After the newdyestuffhas-been reprecipitated from its solution in concentrated sulfuric acidit dyes cotton weak currant shades. By further reaction with 1:5-monobenzoyl-diaminoanthraquinone the bromine atom in ,B-position is alsoexchanged and there is obtained a dyestuff of the probable formula whichdyes cotton in a cold or heated vat violet brown shades of good fastnessto washing and to kier-oiling and of very good fastness to chlorine.

Example 5 4.8 parts of 1:'3-diamino-anthraquinone, 1'7 parts of1-benzoyl-amino-3-bromanthraquinone, 14 parts of anhydrous potassiumacetate, 1 part of copper acetate and 200 parts of nitrobenzene areheated to boiling for 36 hours in a reflux apparatus; the nitrobenzeneis then expelled by distillation with steam and the new product of theprobable formula isolated by filtering the distillation residue. It ispurified by boiling with 5 times its weight of nitrobenzene, stirringuntil cold and filtering cold. The'new dyestuff is thus obtained iii theform of small needles. It dissolves at ordinary temperature in sulfuricacid of 92 per cent strength to a solution which is at first dull violetbut rapidly becomes blue. It dyes cotton in a vat very fastreddish-brownshades. V

Example- 6 18.3 vparts' of 1: 3-dibromanthraquinone, 17.1 parts of1:4-monobenzoyl-diaminoanthraquinone,.,10 parts of anhydrous sodiumacetate, 1 part of copper acetate and 180 parts of nitrobenzene areheated to boiling for 3 hours, whereupon the nitrobenzene is expelledby. distillation with steam and the reaction product, still containingone halogen atom in the molecule, isvisolated by filtration. It issoluble in sulfuric acid of 97 per cent strength to an olive-greensolution.

7.7 parts of the product, 3 parts of l-aminoanthraquinone, 3 parts .ofanhydrous sodium acetate, 0.5 part of copper acetate and 100 parts.

of nitrobenzene are heated to boiling for 18 hours in a refluxapparatus. The reaction mixture is allowed to cool to 50 C. Whilststirring and filtered at this temperature; the solid matter constitutingthe new product of the probable formula is washed with a small quantityof nitrobenzene and boiled with water. The product dissolves in sulfuricacid monohydrate to a grass-green solution. It dyes cotton in a vat'fastwine-red shades.

Example 7 18.3 parts of 1: B-dibromanthraquinone, 11.2 parts ofl-aminoanthraquinone, 12 parts of anhydrous sodium acetate, 1 part ofcopper acetate and 400 parts of nitrobenzene are heated to boiling for 5hours. The reaction mixture is then cooled somewhat, 6 parts of 1:5-diaminoanthraquinone are added and the whole is boiled in a refluxapparatus for a further 18 hours. The solid matter is separated byfiltering at 50 C. and washed with a small quantity of nitrobenzene. Theproduct of the probable formula dissolves in sulfuric acid monohydrateto;a green solution. It dyes cotton in a vat fast'red shades.

Example 8 .74 parts of 1:3'-dibromanthraquinone, 23.8 parts of lzi-diaminoanthraquinone, 25 parts of anhydrous sodium-acetate, 1 part ofcopper acetate, and 800 parts of nitrobenzene are heated to boiling for10 hours. The reaction product is separated by filtering the reactionmixture when cold, and washed, with nitrobenzene and alcohol, and thenextracted with boiling water and dried.

30 parts of the compound thus obtained, which still contains about 16per cent of bromine, are heated to boiling for 22 hours with 20 parts ofl-aminoanthraquinone, 5 parts of anhydrous sodium acetate, 10 parts ofsodium carbonate, :1 part of copper chloride and 600 parts ofnitrobenzene. The reaction product of the probable formula o o =o isfiltered ofi at about 100 C. It is soluble in sulfuric acid monohydrateto a pure green solution, from which violet-brown flakes areprecipitated by pouring into water.

10 parts of this compound are then entered at about 100 C. into a fusionmass which is obtained by adding 20 parts of anhydrous aluminiumchloride to 40 parts of pyridine in such a way that the temperaturedoes. not essentially exceed 100 C. The temperature is then raised untilthe pyridine begins to boil slightly. After 1 hour the fusion mass ispoured into an alkaline sodium hydrosulfite solution whereby the newdyestuff of the probable formula res dissolves to a solution which isyellow-brown. The-solution is then filtered so as toremove smalllifil'tunvatte'd constituents and the. dyestuff' is'separated from the filtrateby vigorous stirring in the air at'ordinary temperature, and isolated byfiltration. It is obtained as a dark powder which dissolves inconcentrated sulfuric acid to a reddish brown-black solution. It dyescotton from the vat blackish-olive shades of very good fastnessproperties.

Example 9 74 parts of 1:3-dibromanthraquinone, 23.8 parts of1:5-diamino-anthraquinone, 25 parts of anhydrous sodium acetate, 1 partof copper acetate and 800 parts of nitrobenzene are heated to boilingfor 10 hours. The reaction product which separates in crystalline formis filtered when cold, washed with nitrobenzene and freed in usualmanner from inorganic constituents. It still contains about 1'7 per centof bromine.

20 parts of the conversion product thus obtained are then heated toboiling for 24 hours with 20 parts of l-amino-anthraquinone, 15 parts ofsodium carbonate, 3 parts of sodium acetate, 1 part of copper chlorideand 200 parts of naphthalene. The whole. then allowed to cool slightly,and 200 parts of chlorobenzene are added. The reaction product isfiltered at about 100, washed with chlorobenzene and worked up as usual.The compound thus obtained of the probable vformula f is thenfurthertreated as follows:

40 parts of aluminium chloride are added so slowly to parts of pyridinethat no boiling of the pyridine occurs, 20 parts of the above newcompound added, and. the whole heated for about 1 hour in a refluxapparatus whilst stirring. The fusion mass is then poured into analkaline hydrosulfite solution whilst still hot, whereby the newdyestuiT goes into solution. The solution is then appropriately filteredto remove portions which have not been vatted, and the filtrate istreated by vigorously stirring in the air. The dyestuif thus obtained ofthe probable formula Example 10 74 parts of 1:3-dibromanthraquinone,23.8 parts of 1:4-diaminoanthraquinone, 25 parts of anhydrous sodiumacetate, 1 part of copper acetate, and 800 parts of nitrobenzene areheated to boiling for 10 hours. When cold, the reaction product isfiltered, the solid matter is washed with nitrobenzene and 7 alcohol,and then extracted with boiling water and dried.

20 parts of the compound thus obtained, which still contains about 16percent of bromine, are now heated to boiling for 24 hours with 20 partsof 1:-mono-benzoyldiamino-anthraquinone, 5 parts of anhydrous sodiumacetate, 10- parts of sodium carbonate, 1 part of copper chloride, and400 parts of nitrobenzene; The reaction product of the probable formula(Dion: NH t B is filtered at about 80 C., washed with nitroben- 7' waythat the temperature does not essentially exceed 100 C. The temperatureis then raised until the pyridine begins to boil slightly. After 1 hourthe fusion mass is poured into an alkaline sodium hydrosulfite solution,whereby the new dyestuff dissolves to a yellow-brown solution. Thedyestufi of the probable formula is precipitated by vigorously stirringin the air at ordinary. temperature, and filtered. It dissolves inconcentrated sulfuric acid to an olive-brown solution. It dyes cottonfrom a vat powerful olivev shades of very good fastness propertiesExample 11 1 gram of the dyestuff made as described in the firstparagraph of Example 1 is well stirredwith cc. of caustic soda solutionof 36 Be. and 100 cc. of water at a temperature of 25-30 (3.; 2 grams ofhydrosulfite concentrated powder are added and vatting is continued forhalf-an-hour at the aforesaid temperature. The dye-bath is prepared with3 cc. of caustic soda solution of 36 B., 1 gram of hydrosulfite andsuificient water-to make up the bath, including the parentvat {to 2liters; the parent vat is then added. The material'is entered at 25-30C. handled for a duarter-of-anhour, grams of sodium chloride or calcinedsodium sulfate are then added, and dyeing is continuedfo'rl hour at-300. The material is then wound off, allowed to oxidize in the air forhalf-an-hour, then rinsed, soured, again rinsed, and soaped at the boil.The material is thus-dyed red-brown.

What we claim is:- v 1. Anthraquinone derivatives of the general formulaO NH-R1 I wherein R1 and R2 represent anthraquinone radicles of which atleast one is diiferent from l-anthraquinonyl, which products form brownto red I 7 to dark powders which dissolve in concentrated sulfuric acidto red to violet to blue to green to black solutions, and dye cottonfrom the vat brown to red to olive tints of very good fastness lproperties.

3. The anthraquinone derivative of the formula NH-O 0 if solution, anddyes cotton from the vat red-brown tints of very good fastnessproperties.

HERMANN HAUSER. MAX BOMMER.

